CN102683747A - Flame-retardant electrolyte for secondary lithium-sulfur battery and preparation method thereof - Google Patents
Flame-retardant electrolyte for secondary lithium-sulfur battery and preparation method thereof Download PDFInfo
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- CN102683747A CN102683747A CN2012101526693A CN201210152669A CN102683747A CN 102683747 A CN102683747 A CN 102683747A CN 2012101526693 A CN2012101526693 A CN 2012101526693A CN 201210152669 A CN201210152669 A CN 201210152669A CN 102683747 A CN102683747 A CN 102683747A
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- electrolyte
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- retardant
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a flame-retardant electrolyte for a secondary lithium-sulfur battery and a preparation method thereof. The electrolyte is prepared by adding a phosphorus-containing flame retardant on the basis of the conventional lithium ion electrolyte, and the flame retardant accounts for 1-50 percent by mass of the total weight of the electrolyte. The invention further discloses a secondary lithium-sulfur battery prepared by using an electrolyte which contains an appropriate amount of flame-retardant additive. According to charging and discharging tests at the voltage of 1.0-3.0V, the electrochemical performance is not influenced, and the volume keeping rate is high after 50 cycles; and moreover, the flammability of the electrolyte is lowered greatly, and the safety performance of the lithium-sulfur battery can be enhanced.
Description
Technical field
The present invention relates to secondary lithium-sulfur cell electrolyte system, particularly a kind of flame-retardant electrolyte that is used for the secondary lithium-sulfur cell and preparation method thereof, and by the lithium-sulfur cell of flame-retardant electrolyte assembling.
Background technology
Conventional lithium ion battery receives the restriction of its positive electrode capacity, lower (the about 150Wh kg of energy density
-1), can't satisfy the demand of Large Electric car, and chargeable lithium-sulfur cell has appreciable theoretical energy density (2600Whkg
-1).But being applied to reality, lithium-sulfur cell also need consider the safety issue that is similar to traditional lithium ion battery existence.At first, the electrolyte of lithium-sulfur cell adopts ether organic solvent now mostly, as 1; 3-dioxolane (DOL) and glycol dimethyl ether (DME), also some adopts the carbonates organic solvent, but boiling point is all lower; Inflammable, under battery abuse state, there is the danger of blast on fire.Secondly, lithium-sulfur cell is made negative pole with lithium metal, and the reaction between itself and the organic solvent and the formation of Li dendrite all can influence the fail safe of battery.At last, positive electrode is to be composited by conductive carbon material and sulphur simple substance mostly, and both's easy firing has weakened battery security.Being similar to traditional lithium ion battery adopts phosphonium flame retardant electrolyte to strengthen the method for fail safe; In lithium-sulfur cell electrolyte, add the combustibility that amount of retardant can reduce electrolyte; Thereby improve the security performance of lithium-sulfur cell, eliminate because of in battery, using the potential safety hazard that liquid electrolyte exists.
What study at most in the lithium-ion battery electrolytes flame-retardant additive is that phosphorus is based flame retardant; Like the alkyls phosphate: trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), triphenyl phosphate (TPP) etc.; And the haloalkyl kind phosphate ester is as three (2; 2, the 2-trifluoroethyl) phosphite ester (TTEP).Chinese patent CN1558464A discloses one type of fire retardant as the lithium-ion battery electrolytes cosolvent, and (TBP), this based flame retardant is influential to chemical property for TMP, TEP, and the specific capacity of battery circulation slightly reduces.Chinese patent CN101702445A discloses a kind of fire retardant (dimethyl methyl phosphonate) that is used for lithium-ion battery electrolytes; This fire retardant does not have influence to battery performance; To the good flame retardation effect of electrolyte, but do not see any report that is applied to lithium-sulfur cell about flame-retardant additive.It is good to select with sulphur positive electrode compatibility, and little to the battery performance influence, good flame retardation effect and cheap fire retardant are starting points of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of secondary lithium-sulfur cell anti-flammability electrolyte and preparation method thereof, and by the lithium-sulfur cell of this flame-retardant electrolyte assembling.Fire retardant and sulphur positive electrode compatibility that anti-flammability electrolyte of the present invention adopts are good, and be little to the battery performance influence, good flame retardation effect and cheap.
The objective of the invention is to realize through following technical scheme:
First aspect the present invention relates to a kind of secondary lithium-sulfur cell anti-flammability electrolyte, and said anti-flammability electrolyte comprises lithium salts, organic solvent and fire retardant; The mass percentage content that said fire retardant accounts for the flame-retardant electrolyte gross weight is 1%～50%.
Preferably, said fire retardant is a phosphonium flame retardant.
Further preferably; Said phosphonium flame retardant is trimethyl carbonate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), triphenyl phosphate (TPP), dimethyl methyl phosphonate (DMMP), triphenyl phosphite (TPP (i)), Trimethyl phosphite (TMP (i)), three (2; 2,2-trifluoroethyl) one or more in the phosphite ester (TTEP).
Preferably, said lithium salts is LiPF
6, LiBF
4, dioxalic acid lithium borate (LiBOB), LiClO
4, LiCF
3SO
3Or LiN (CF
3SO
2)
2
Preferably, said organic solvent is one or more in carbonates, the ether organic solvent.
Further preferably, said carbonates organic solvent is ethylene carbonate (EC), propene carbonate (PC), ethyl-methyl carbonic ester (EMC), dimethyl carbonate (DMC) or diethyl carbonate (DEC).
Further preferably, said ether organic solvent is dioxolane (DOL), glycol dimethyl ether (DME), diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
Second aspect the present invention relates to a kind of preparation method of aforesaid secondary lithium-sulfur cell anti-flammability electrolyte, comprises the steps:
A, lithium salts is dissolved in the organic solvent, obtains the electrolyte that concentration is 0.5～2mol/L;
B, in the electrolyte that step a obtains, add fire retardant, obtain flame-retardant electrolyte; The mass percentage content that said fire retardant accounts for the flame-retardant electrolyte gross weight is 1%～50%.
Preferably, said fire retardant is a phosphonium flame retardant.
The third aspect the present invention relates to a kind of secondary lithium-sulfur cell by aforesaid anti-flammability electrolyte assembling, and the sulfenyl material that it uses is elemental sulfur S
8, many lithium sulfides, sulfenyl composite material, organosulfur compound or carbon sulphur polymer;
Said many lithium sulfides chemical formula is: Li
2S
n, wherein, 1≤n≤8;
Said carbon sulphur polymer chemistry formula is: (C
2S
x)
n, wherein, x is 2～20, n>=2;
Said sulfenyl composite material is: elemental sulfur and polyacrylonitrile are by mass ratio 4～16: 1 mix after, under nitrogen protection, be heated to 250～400 ℃ and be incubated and obtained in 1～16 hour.
The beneficial effect that the present invention has is: the electrolyte combustibility of adding organic phosphorus compounds additive reduces greatly, and is also less to the influence of conductivity; With the secondary lithium-sulfur cell that the electrolyte that contains organic phosphorus fire retardant is assembled, chemical property is influenced hardly, can reach the purpose of taking into account flame retardant effect and chemical property.
Description of drawings
Fig. 1 is the self-extinguishing time curve chart that contains the electrolyte of different content DMMP;
Fig. 2 is the curve chart of electrolytic conductivity with the DMMP content;
Fig. 3 is the AC impedance figure that open circuit is surveyed down after being circulated for the second time by the lithium-sulfur cell that the electrolyte of different DMMP content is assembled;
Fig. 4 is the lithium-sulfur cell charging and discharging curve figure second time by the electrolyte assembling of different DMMP content;
Fig. 5 is the cyclic curve figure by the lithium-sulfur cell of the electrolyte assembling of different DMMP content.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some adjustment and improvement.These all belong to protection scope of the present invention.
Embodiment 1
In glove box, evenly mix EC and EMC in 1: 1 by volume, in this mixed solvent, add LiPF
6, stir, process the electrolyte that concentration is 1mol/L.In this electrolyte, add fire retardant DMMP again, flame-retardant electrolyte, be that the mass percentage content that said DMMP accounts for the flame-retardant electrolyte gross weight is respectively 7%, 11%, 15%, 21%, 30%, 50%.
Embodiment 2
In glove box, evenly mixed EC in 1: 1: 1 by volume, PC with DEC, adds LiPF in this mixed solvent
6, stir, process the electrolyte that concentration is 0.5mol/L.In this electrolyte, add Firemaster TT EP again, get flame-retardant electrolyte, the mass percentage content that said TTEP accounts for the flame-retardant electrolyte gross weight is respectively 1%, 7%, and 11%, 15%, 21%, 30%, 50%.
Embodiment 3
In glove box, evenly mix DOL and DMC in 1: 1 by volume, in this mixed solvent, add LiN (CF
3SO
2)
2, stir, process the electrolyte that concentration is 2mol/L.In this electrolyte, add fire retardant TPP (i) and TPP (the two volume ratio is 1: 1) again, get flame-retardant electrolyte, the mass percentage content that said TPP (i) accounts for the flame-retardant electrolyte gross weight is respectively 1%, 7%, and 11%, 15%, 21%, 30%, 50%.
Embodiment 4, flammable test
With self-extinguishing time (self-extinguishing time), be called for short SET, estimate the combustibility of each electrolyte among the embodiment 1.Concrete steps are that glass fibre cotton is processed the cotton balls that diameter is about 1mm; Absorb the electrolyte of 0.2～0.3g and the electrolyte quality that weighing absorbs; Light cotton balls with alcolhol burner, burning time is controlled in the 1s, removes and write down the time of removing alcolhol burner to fray-out of flame rapidly.Self-extinguishing time divided by the electrolyte quality that absorbs, is obtained standardized self-extinguishing time.
The combustibility of electrolyte in the test implementation example 1 according to the method described above, the result sees Fig. 1.After adding the DMMP of 7wt%, the self-extinguishing time of electrolyte promptly is reduced to 37s/g from 104s/g.Along with the increase of DMMP content, the self-extinguishing time of electrolyte reduces gradually, and when DMMP content increases to about 11wt%, electrolyte burns hardly.
Be respectively 0%, 7% with DMMP content under the conductivity measurement test room temperature, the conductivity of 11%, 15%, 21% electrolyte (electrolyte of embodiment 1) is judged the influence of DMMP to electrolytic conductivity.With electrolyte pour into respectively inlab710 conductivity test pool (Metter Toledo, Switzerland) in, with its conductivity of FE30 conductivity meter test, the result sees Fig. 2.By shown in Figure 2, DMMP is less to the conductivity influence of blank electrolysis liquid.
Embodiment 6, be assembled into battery and carry out electrochemical property test
The preparation of positive electrode: with the sulfenyl material, conductive carbon Super P, binding agent PTFE evenly mix in proportion at 70: 20: 10; Add an amount of ethanol and disperse, heat up and boil off unnecessary solvent, roll film forming with roll squeezer; Make the disk of diameter 12mm, be pressed on the nickel foam.This sulfenyl material for the sulfenyl composite material is: elemental sulfur and polyacrylonitrile (can be 4～16: after arbitrary value in 1) mixing, under nitrogen protection, be heated to 300 ℃ (can be arbitrary value in 250～400 ℃) and be incubated 12 hours that (can be arbitrary value in 1～16 hour) obtain by mass ratio 10: 1.
The assembling of battery and test: with ENTEK PE film is barrier film; The lithium sheet is a negative pole; DMMP content is respectively 11%, 21% electrolyte (electrolyte among the embodiment 1) and blank electrolysis liquid, and the anodal 2016 type button cells of forming of sulfenyl; Between 1.0～3.0V, carry out charge-discharge test, with the AC impedance of CHI604D electrochemical workstation test battery under open circuit voltage.
It is as shown in Figure 3 to charge and discharge circulation each button cell impedance after twice.Along with the increase of DMMP content, the electrode/electrolyte interface impedance obviously increases, and particularly when DMMP content was 21%, electrochemical impedance sharply increased.Secondary charging and discharging curve is as shown in Figure 4, and along with the increase of DMMP content, polarization obviously increases, and when DMMP content reached 21%, voltage difference obviously increased.Fig. 3 and Fig. 4 explain that the content of DMMP should be controlled in certain scope, otherwise can influence the chemical property of battery.Repeatedly the result of charge-discharge test is as shown in Figure 5, and when DMMP content was low, cyclical stability was influenced hardly.When the DMMP addition was 11%, electrolyte burnt hardly, and chemical property is unaffected simultaneously.
Claims (10)
1. a secondary lithium-sulfur cell anti-flammability electrolyte is characterized in that said anti-flammability electrolyte comprises lithium salts, organic solvent and fire retardant; The mass percentage content that said fire retardant accounts for the flame-retardant electrolyte gross weight is 1%～50%.
2. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 1 is characterized in that said fire retardant is a phosphonium flame retardant.
3. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 2; It is characterized in that; Said phosphonium flame retardant is trimethyl carbonate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, dimethyl methyl phosphonate, triphenyl phosphite, Trimethyl phosphite, three (2; 2,2-trifluoroethyl) one or more in the phosphite ester.
4. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 1 is characterized in that said lithium salts is LiPF
6, LiBF
4, LiBOB, LiClO
4, LiCF
3SO
3Or LiN (CF
3SO
2)
2
5. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 1 is characterized in that said organic solvent is one or more in carbonates, the ether organic solvent.
6. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 5 is characterized in that said carbonates organic solvent is ethylene carbonate, propene carbonate, ethyl-methyl carbonic ester, dimethyl carbonate or diethyl carbonate.
7. secondary lithium-sulfur cell anti-flammability electrolyte according to claim 5 is characterized in that said ether organic solvent is dioxolane, glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
8. the preparation method of a secondary lithium-sulfur cell anti-flammability electrolyte as claimed in claim 1 is characterized in that, comprises the steps:
A, lithium salts is dissolved in the organic solvent, obtains the electrolyte that concentration is 0.5～2mol/L;
B, in the electrolyte that step a obtains, add fire retardant, obtain flame-retardant electrolyte; The mass percentage content that said fire retardant accounts for the flame-retardant electrolyte gross weight is 1%～50%.
9. the preparation method of secondary lithium-sulfur cell anti-flammability electrolyte according to claim 8 is characterized in that said fire retardant is a phosphonium flame retardant.
10. the secondary lithium-sulfur cell by the described anti-flammability electrolyte assembling of claim 1 is characterized in that the sulfenyl material that uses is elemental sulfur S
8, many lithium sulfides, sulfenyl composite material, organosulfur compound or carbon sulphur polymer;
Said many lithium sulfides chemical formula is: Li
2S
n, wherein, 1≤n≤8;
Said carbon sulphur polymer chemistry formula is: (C
2S
x)
n, wherein, x is 2～20, n>=2;
Said sulfenyl composite material is: elemental sulfur and polyacrylonitrile are by mass ratio 4～16: 1 mix after, under nitrogen protection, be heated to 250～400 ℃ and be incubated and obtained in 1～16 hour.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326064A (en) * | 2013-05-24 | 2013-09-25 | 中国科学技术大学 | A safe lithium ion battery electrolyte |
| CN103326063A (en) * | 2013-05-18 | 2013-09-25 | 贵州航天电源科技有限公司 | Lithium ion battery flame-retardant electrolyte and preparation method thereof |
| CN104393341A (en) * | 2014-10-15 | 2015-03-04 | 合肥彩象信息科技有限公司 | Highly safe electrolyte of lithium battery |
| CN105659423A (en) * | 2013-10-21 | 2016-06-08 | 巴斯夫欧洲公司 | Flame retardant for electrolytes for batteries |
| CN105789683A (en) * | 2016-03-22 | 2016-07-20 | 山东大学 | Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor |
| CN105977533A (en) * | 2016-04-19 | 2016-09-28 | 上海交通大学 | Flame-retardant electrolyte for secondary lithium-sulfur battery and preparation method for flame-retardant electrolyte |
| CN105977534A (en) * | 2016-06-21 | 2016-09-28 | 上海交通大学 | Functional electrolyte for secondary lithium-sulfur battery and preparation method thereof |
| WO2017185479A1 (en) * | 2016-04-29 | 2017-11-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Material with core-shell structure, preparation method therefor and use thereof |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN108899582A (en) * | 2018-07-10 | 2018-11-27 | 中国科学院长春应用化学研究所 | A kind of flame retardant type electrolyte and Dual-ion cell |
| CN109599592A (en) * | 2018-11-07 | 2019-04-09 | 上海交通大学 | A kind of secondary lithium-sulfur battery intrinsic safety electrolyte and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326063A (en) * | 2013-05-18 | 2013-09-25 | 贵州航天电源科技有限公司 | Lithium ion battery flame-retardant electrolyte and preparation method thereof |
| CN103326064A (en) * | 2013-05-24 | 2013-09-25 | 中国科学技术大学 | A safe lithium ion battery electrolyte |
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| CN104393341A (en) * | 2014-10-15 | 2015-03-04 | 合肥彩象信息科技有限公司 | Highly safe electrolyte of lithium battery |
| CN105789683A (en) * | 2016-03-22 | 2016-07-20 | 山东大学 | Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor |
| CN105977533A (en) * | 2016-04-19 | 2016-09-28 | 上海交通大学 | Flame-retardant electrolyte for secondary lithium-sulfur battery and preparation method for flame-retardant electrolyte |
| CN107331856B (en) * | 2016-04-29 | 2019-12-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Core-shell structure material, preparation method and application thereof |
| WO2017185479A1 (en) * | 2016-04-29 | 2017-11-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Material with core-shell structure, preparation method therefor and use thereof |
| CN107331856A (en) * | 2016-04-29 | 2017-11-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Material, its preparation method and the application of core shell structure |
| CN105977534A (en) * | 2016-06-21 | 2016-09-28 | 上海交通大学 | Functional electrolyte for secondary lithium-sulfur battery and preparation method thereof |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN108899582A (en) * | 2018-07-10 | 2018-11-27 | 中国科学院长春应用化学研究所 | A kind of flame retardant type electrolyte and Dual-ion cell |
| CN108899582B (en) * | 2018-07-10 | 2021-05-04 | 中国科学院长春应用化学研究所 | Flame-retardant electrolyte and dual-ion battery |
| CN109599592A (en) * | 2018-11-07 | 2019-04-09 | 上海交通大学 | A kind of secondary lithium-sulfur battery intrinsic safety electrolyte and preparation method thereof |
| CN109599592B (en) * | 2018-11-07 | 2022-07-15 | 上海交通大学 | Intrinsic safety electrolyte for secondary lithium-sulfur battery and preparation method thereof |
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Application publication date: 20120919 |